KR20130134483A - Olefin resin composition and encapsulant of optoelectronic device - Google Patents

Abstract

Embodiments of the present invention relate to an olefin resin composition, an encapsulant, and an optoelectronic device, which are used as encapsulants of various optoelectronic devices to provide an olefin resin composition exhibiting excellent adhesion to the front substrate and the back sheet included in the device. Can be. In addition, it is possible to provide an olefin resin composition capable of maintaining excellent workability and economical efficiency of device manufacturing without adversely affecting parts and working environments such as an optoelectronic device or a wiring electrode encapsulated in an optoelectronic device.

Description

Olefin Resin Composition and Encapsulant of Optoelectronic Device

Embodiments of the present invention relate to an olefin resin composition and an encapsulant for an optoelectronic device.

Optoelectronic devices, such as photovoltaic cells, light emitting diodes (LEDs), or organic LEDs, are encapsulating materials that encapsulate the light emitting or photosensitive sites of the device ( Encapsulant).

For example, in the solar cell module, a lamination method in which a transparent front substrate, an encapsulant, a photovoltaic element, an encapsulant, and a back sheet, which are typically light-receiving substrates, are laminated, and then heat-compressed while vacuum-stacking the laminate. It can be prepared by.

As the encapsulant used for the solar cell module, EVA (ethylene-vinyl acetate) resin is most used in view of processability, workability and cost.

However, EVA resin is low in adhesive strength with an element included in an optoelectronic device such as a front substrate or a back sheet and in contact with the encapsulant. Therefore, if the module is exposed to the outdoors for a long time, there is a problem that the delamination easily occurs. In addition, in the process of manufacturing a solar cell module using an encapsulant including an EVA resin, the EVA resin may be thermally decomposed depending on heat compression conditions, and acetic acid gas may be generated. Such an acetic acid gas not only deteriorates the working environment, but also adversely affects photovoltaic elements or electrodes included in the solar cell module, and also causes deterioration of the module and deterioration of power generation efficiency.

Accordingly, there is a continuing need for encapsulants for optoelectronic devices with improved long-term adhesion properties.

Embodiments of the present invention provide an olefin resin composition and an encapsulant for an optoelectronic device with improved adhesive strength.

An aspect according to one embodiment of the present invention comprises an olefin resin, an unsaturated silane compound including a vinyl group, a hydrolysis catalyst and a radical initiator, wherein the hydrolysis catalyst is 0.001 to 1 part by weight based on 100 parts by weight of the olefin resin. It is related with the olefin resin composition containing.

Aspects according to another embodiment of the invention are directed to an olefin resin composition comprising a silane-modified olefin resin and a hydrolysis catalyst.

An aspect according to another embodiment of the present invention relates to an encapsulant for an optoelectronic device including the olefin resin composition and a method of manufacturing the same. The olefin resin composition may include a hydrolysis catalyst to convert the silanol group by hydrolysis-promoting alkoxy groups of the silane-modified olefin resin in the manufacture of an optoelectronic device, thereby improving the adhesion of the optoelectronic device to the front substrate or the back sheet. Make sure

An aspect according to another embodiment of the present invention relates to an optoelectronic device including the encapsulant and a method of manufacturing the same.

Hereinafter, embodiments of the present invention will be described in more detail. In addition, in describing the present invention, detailed descriptions of related well-known general configurations or functions are omitted.

The olefin resin composition according to one embodiment of the present invention includes an olefin resin, an unsaturated silane compound including a vinyl group, a hydrolysis catalyst, and a radical initiator.

The unsaturated silane compound including a vinyl group included in the olefin resin composition is an unsaturated silane compound represented by Formula 1 below, and may be grafted to an olefin resin such as polyolefin in the presence of a radical initiator to prepare a silane-modified olefin resin. have. That is, the graft polymer in which the unsaturated silane compound represented by the following Formula 1 is grafted to the olefin resin may be prepared.

[Formula 1]

DSi (X) _m Y _(3-m)

In Formula 1, D represents alkenyl as bonded to a silicon atom, X represents a reactive functional group bonded to a silicon atom, Y represents a non-reactive functional group bonded to a silicon atom, m is 1 to 3 Represents an integer.

D in Formula 1 may be vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl or γ-methacryloxypropyl, and the like, and may be vinyl.

The reactive functional group (X) is a functional group that can be hydrolyzed by a hydrolysis catalyst, specifically, an alkoxy group, phenoxy group, alkylthio group, aryloxy group, acyloxy group, halogen group, amine group or alkyl It may be a lenoxythio group. In this case, examples of the alkoxy group include alkoxy groups having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, and examples of the acyloxy group include acyloxy groups having 1 to 12 carbon atoms. Examples of the alkylthio group include an alkylthio group having 1 to 12 carbon atoms, and examples of the alkyleneoxythio group include an alkyleneoxythio group having 1 to 12 carbon atoms.

In one embodiment, X in Chemical Formula 1 may be an alkoxy group, specifically, may be an alkoxy group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, and in another embodiment, an alkoxy group having 1 to 4 carbon atoms. For example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, butoxy group etc. can be mentioned, For example, a methoxy group or an ethoxy group etc. can be used in some embodiments.

In addition, the non-reactive functional group of Formula 1 may be hydrogen, an alkyl group, an aryl group or an aralkyl group. In the above, the alkyl group may be, for example, an alkyl group having 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms. The aryl group in Y may be an aryl group having 6 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms, for example, a phenyl group, and the aralkyl group may be an aralkyl having 7 to 19 carbon atoms or an aralkyl having 7 to 13 carbon atoms, for example, benzyl. It may be a flag.

In addition, in Formula 1, m is an integer of 1 to 3, in some embodiments may be 3.

Specific examples of the unsaturated silane compound of Formula 1 may be vinyl alkoxy silane. For example, the unsaturated silane compound is vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl tributoxy silane, vinyl tripentoxy silane, vinyl triphenoxy Silane, vinyltriacetoxy silane, and the like, and the like, and examples thereof include, but are not limited to, vinyltrimethoxy silane or vinyltriethoxy silane.

The olefin resin composition according to the embodiments of the present invention may include 0.1 to 5.0 parts by weight or 0.5 to 3.0 parts by weight of the unsaturated silane compound of Formula 1 based on 100 parts by weight of the olefin resin. Within such a range, the adhesion of the olefin resin composition, for example, adhesion to a glass substrate, a back sheet, and the like can be maintained excellent.

Unless otherwise specified, unit weight parts herein means weight ratios.

In addition, in embodiments of the present invention, the olefin resin is ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-phenyl-1-butene, 6-phenyl-1-hexene, 2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 4- Α, such as methyl-1-hexene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene or vinylcyclohexane -Olefins, dienes such as 1,3-butadiene, 1,4-butadiene, 1,5-hexadiene, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1 Halogen-substituted α-olefins such as, 1-difluoroethylene, 3-fluoropropene, trifluoroethylene or 3,4-dichloro-1-butene, cyclopentene, cyclohexene, norbornene, 5-methylnor Cyclic olefins such as bonene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene or 5-benzylnorbornene May be a homopolymer or copolymer of olefin monomers least one housing, without being limited thereto.

For example, the olefin resin may be polyethylene, polypropylene or ethylene-vinylacetate copolymer, and in one embodiment may be polyethylene.

The polyethylene is a polyolefin containing ethylene in a polymerized form as a main component, and specifically, α having three or more carbon atoms while including not only a homopolymer of ethylene but also at least 50 mol% or more of ethylene in a polymerized unit. Copolymers containing olefins or other comonomers as polymerized units may also be included. The polyethylene may be, for example, one or more of low density polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, ultralow low density polyethylene or linear low density polyethylene.

As polyethylene to which an unsaturated silane compound is grafted, polyethylene with many side chains can be used. Grafting can be performed more efficiently in polyethylene having many side chains. Polyethylene having a large number of side chains generally has a low density, and a polyethylene having a small side chain generally has a high density. Thus, the use of low density polyethylene can increase the grafting efficiency, specifically a polyethylene having a density of 0.85 g / cm ³ to 0.92 g / cm ³ , or a density of about 0.85 g / cm ³ to 0.90 g / cm ³ Can be used.

In addition, the polyethylene has a melt flow rate (MFR) of about 1.0 g / 10 minutes to about 10.0 g / 10 minutes, about 1.0 g / 10 minutes to 8.0 g / 10 minutes, or about 3.0 g / 10 minutes at 190 ° C. To 7.0 g / 10 minutes. When having the MFR in this range, for example, the olefin resin composition may exhibit excellent moldability and the like.

The olefin resin composition according to embodiments of the present invention includes a hydrolysis catalyst. The hydrolysis catalyst is a silanol group (Si- OH) and the like, and the silanol group converted by the hydrolysis catalyst forms a chemical covalent bond through a condensation reaction with a functional group such as a hydroxyl group on the front substrate in contact with the encapsulant of the optoelectronic device. It is possible to improve the properties, and to form a strong hydrogen bond with the fluorine of the back sheet comprising a surface layer containing a fluoropolymer can improve the adhesion.

In addition, the hydrolysis catalyst can stably maintain the physical properties of the composition as intended without adversely affecting other components included in the composition, for example, UV stabilizers as described below. The conversion of the silane-modified olefin resin to hydrolysates, such as silanol groups, of reactive functional groups can take place in a vacuum lamination step for the production of optoelectronic devices, but in order to give sufficient adhesive strength, for example, before the vacuum lamination step, In the rafting extrusion step, a hydrolysis catalyst may be added to advance the conversion to a larger amount of silanol groups, thereby exhibiting better adhesion strength with the surface of the glass substrate and the back sheet during optoelectronic device fabrication. The conversion of such reactive functional groups to hydrolysates such as silanol groups by hydrolysis catalysts, for example, conversion of -Si-O-CH ₃ to -Si-OH is more than in the absence of a hydrolysis catalyst. The conversion of -Si-O-CH ₃ to -Si-OH occurs.

That is, when the olefin resin composition according to the embodiments of the present invention is used as the encapsulant of the optoelectronic device, the hydrolysis catalyst is a hydroxyl group and the like in which the reactive functional group of the silane-modified olefin resin is present on the surface of the front substrate such as the glass substrate. By forming a chemical or physical bond with the functional groups of and, in particular, the fluorine present on the surface of the back sheet, it is possible to improve the adhesion to the front substrate and the back sheet of the encapsulant of the optoelectronic device.

Hydrolysis catalysts that can be used in embodiments of the present invention can catalyze the conversion of hydrolyzates (eg silanol groups) by hydrolysis of reactive silyl groups (eg alkoxy silane groups). As long as it is not limited.

For example, an acid catalyst may be used as the hydrolysis catalyst, and specifically, general inorganic and organic acids may be used. Examples of the inorganic acid may include hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid. Or chromic acid. Examples of organic acids include stearic acid, acetic acid, sulfonic acid, citric acid, lactic acid, and gluconic acid. ), Glycolic acid, succinic acid, oxalic acid, benzoic acid, benzoic acid, tartaric acid, fumaric acid, mandelic acid, propionic acid acid, Maleic acid, Galacturonic acid, Glutamic acid, Glutaric acid, Glucuronic acid, Aspartic acid, Ascorbic acid acid, Carboxylic acid, Vanilic acid (Va) nillic acid) or hydroiodic acid. The hydrolysis catalysts can be used alone or in combination.

The hydrolysis catalyst may be included in an amount of 0.001 to 1 parts by weight, or 0.01 to 0.1 parts by weight based on 100 parts by weight of the olefin resin in the olefin resin composition. In such a weight ratio, it is possible to effectively control the physical properties of the resin composition, increase the adhesion between the front substrate and the back sheet, and also maintain excellent activity of other additives included in the resin composition. This is because when the amount of the hydrolysis catalyst added is excessive, it can act as an impurity that can decompose the olefin resin or induce side reactions in addition to the desired catalytic action.

The olefin resin composition according to the embodiments of the present invention includes a radical initiator. The radical initiator may serve to initiate a reaction in which an unsaturated silane compound is grafted to the olefin resin.

The radical initiator is not particularly limited as long as it can initiate radical polymerization of a vinyl group, and examples thereof include one or two or more selected from the group consisting of organic peroxides, hydroperoxides and azo compounds. Specifically, t-butyl cumyl peroxide, di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl Dialkyl peroxides such as -2,5-di (t-butylperoxy) -3-hexine; Hydroperoxides such as cumene hydroperoxide, diisopropyl benzene hydroperoxide, 2,5-dimethyl-2,5-di (hydroperoxy) hexane and t-butylhydroperoxide; Diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide and 2,4-dichlorobenzoyl peroxide; butyl peroxy isobutyrate, t-butyl peroxyacetate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyoctoate, t- Butyl peroxybenzoate, di-t-butylperoxy phthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl- (Benzoyl peroxy) -3-hexyne; And azo compounds such as ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, lauryl peroxide, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile). One or more selected from, but is not limited thereto.

Such a radical initiator may be included in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the olefin resin.

The olefin resin composition according to the embodiments of the present invention may further include one or more additives selected from light stabilizers, UV absorbers, heat stabilizers, and the like, as necessary.

The light stabilizer may serve to prevent photooxidation by capturing the active species of the photodegradation start of the olefin resin depending on the use to which the composition is applied. The kind of light stabilizer that can be used is not particularly limited, and for example, a known compound such as a hindered amine compound or a hindered piperidine compound can be used.

According to the use of the composition, the UV absorber may play a role of absorbing ultraviolet rays from sunlight or the like, converting them into harmless thermal energy in the molecule, and preventing the active species of photodegradation initiation in the olefin resin from being excited. . The specific kind of UV absorber that can be used is not particularly limited, and for example, inorganic UV such as benzophenone series, benzotriazole series, acrylonitrile series, metal complex salt system, hindered amine series, ultrafine titanium oxide or ultrafine zinc oxide, etc. One kind or a mixture of two or more kinds such as an absorbent may be used.

Examples of the heat stabilizer include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetra Kiss (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4-diylbisphosphonate and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite Phosphorus thermal stabilizers; Lactone-type heat stabilizers, such as the reaction product of 8-hydroxy-5,7-di-tert- butyl-furan-2-one and o-xylene, are mentioned 1 type, or 2 or more types can be used. have.

In the olefin resin composition, the content of the light stabilizer, UV absorber and / or heat stabilizer is not particularly limited. That is, the content of the additive can be appropriately selected in consideration of the use of the resin composition, the shape and density of the additive, and the like, and is usually suitably within the range of 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the total solid content of the resin composition. Can be adjusted.

In addition to the above components, the olefin resin composition according to the embodiments of the present invention may appropriately further include various additives known in the art, depending on the use to which the resin component is applied.

The olefin resin composition according to other embodiments of the present invention may include a silane-modified olefin resin and a hydrolysis catalyst. The silane-modified olefin resin may be formed by grafting an unsaturated silane compound represented by Formula 1 on an olefin resin, and may be, for example, an olefin resin having a reactive silyl group represented by Formula 2 below.

As used herein, the term "reactive silyl group" means a silyl group having a reactive functional group capable of physical or chemical interaction with another functional group or having a functional group capable of providing such a functional group.

[Formula 1]

-Si (X) _m Y _(3-m)

In Formula 2, X is bonded to a silicon atom, and an alkoxy group, phenoxy group, alkylthio group, aryloxy group, acyloxy group, halogen group, amine group, alkyleneoxythio group or any one of the above Represent decomposition products,

Y is bonded to a silicon atom and represents hydrogen, an alkyl group, an aryl group or an aralkyl group

m represents the integer of 1-3.

The hydrolysis catalyst included in the olefin resin composition is the same as described above, and promotes a hydrolysis reaction such as an alkoxy group of the reactive silyl group to help the conversion to silanol groups.

The olefin resin composition according to the embodiments of the present invention may further include an olefin resin for addition as necessary. The specific kind of the olefin resin for addition that can be used in the embodiments of the present invention is not particularly limited. For example, polyethylene may be used as the olefin resin for addition, and specifically, polyethylene belonging to the same category as polyethylene exemplified as the unsaturated silane compound may be used.

The content of the olefin resin for addition is not particularly limited and may be selected in consideration of the desired physical properties. For example, the addition olefin resin may be included in the range of 0.01 parts by weight to 3000 parts by weight, or 90 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the olefin resin.

Still other embodiments of the present invention relate to an encapsulant including the olefin resin composition as described above. The olefin resin composition may be used as an encapsulant encapsulating an element in various optoelectronic devices, but is not limited thereto. For example, the olefin resin composition may also be used as an industrial material applied to an elevated temperature lamination process.

The said sealing material may contain the olefin resin composition in the state which each component is mixed uniformly in the state, and is contained in the state shape | molded by various shaping | molding methods, such as hot melt extrusion and T die shaping | molding. There may be.

The shape of the encapsulant is not particularly limited, and may be, for example, a sheet or a film. In this case, the thickness of the encapsulant may be adjusted to about 10 μm to 2,000 μm, or about 100 μm to 1250 μm, in consideration of the element's support efficiency and the possibility of breakage, the weight reduction and workability of the device, and the like. However, the thickness of the encapsulant may vary depending on the specific application applied.

The method for producing the encapsulation material for an optoelectronic device is not particularly limited. First, the step of preparing an olefin resin composition as described above, which may include the step of preparing a silane-modified olefin resin.

The method for producing the silane-modified olefin resin is not particularly limited, but there are two methods. For example, a silane-modified olefin resin is prepared by adding an olefin resin such as polyethylene, the unsaturated silane compound to the reactor, mixing in the reactor, and then grafting the unsaturated silane compound to the olefin resin in the presence of a suitable radical initiator. You may.

The type of the reactor in which the silane-modified olefin resin is produced is not particularly limited as long as the target resin can be produced by reacting the reactant in a hot melt or liquid state. For example, the reactor may be a cylinder with an extruder or a hopper. In the case of using such a reactor, for example, a liquid unsaturated silane compound and a radical initiator are extruded into a heat-melted olefin resin through an extruder, or an olefin resin, a radical initiator and an unsaturated silane compound are mixed in a hotter. After the addition, the silane-modified olefin resin can also be produced by reacting by heating and melting in a cylinder.

The radical initiator is not particularly limited as long as it can initiate radical polymerization of a vinyl group, and examples thereof include one or two or more kinds of organic peroxides, hydroperoxides, or azo compounds. Specifically, t-butyl cumyl peroxide, di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl- Dialkyl peroxides such as 2,5-di (t-butylperoxy) -3-hexyne, cumene hydroperoxide, diisopropyl benzene hydroperoxide, 2,5-dimethyl-2,5-di (hydro Hydroperoxides such as peroxy) hexane and t-butyl hydroperoxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, 2, Diacyl peroxides such as 4-dichlorobenzoyl peroxide, t-butylperoxy isobutylate, t-butylperoxy acetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy pibarate, t-butylperoxy octoate, t-butylperoxyisopropyl carbonate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, 2,5-di Peroxy esters such as methyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) -3-hexine, methethyl ketone peroxide, cyclohexanone And at least one selected from the group consisting of azo compounds such as ketone peroxides such as peroxide, lauryl peroxide, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile).

The said olefin resin composition can be manufactured by mixing a hydrolysis catalyst with the silane modified olefin resin manufactured as mentioned above. Such a hydrolysis catalyst may be added into the reactor before or after the silane-modified olefin resin is formed, in which case, other additives such as UV absorbers, heat stabilizers or UV stabilizers may be added together. .

As such, the process may be simplified by simultaneously preparing the silane-modified olefin resin and mixing the additives in one reactor.

In the above, the hydrolysis catalyst and / or other additives may be introduced into the reactor as it is or mixed in a form of a master batch. In the above, the master batch refers to a pellet-shaped raw material in which the additives to be added are concentrated and dispersed at a high concentration, and in particular, in processing and molding plastic raw materials by extrusion or injection method, a specific function is applied to the finished product. Used to introduce additives.

The method of introducing an additive such as a hydrolysis catalyst into the reactor in which the silane-modified olefin resin is formed is not particularly limited. For example, a side feeder may be installed at an appropriate position of an extruder or a cylinder, and the feeder A method of adding an additive in the form of a master batch or mixing and adding an olefin resin or the like in a hopper may be used.

In the above method, the specific type and design of the reactor, the conditions such as the heating and melting, the mixing or the temperature and time of the reaction, the production method of the master batch is not particularly limited, and may be appropriately selected in consideration of the raw materials used and the like. have.

In embodiments of the present invention, the encapsulant for an optoelectronic device may be manufactured by molding the olefin resin composition prepared as described above into a film or sheet shape. Such a molding method is not particularly limited, and for example, the encapsulant may be manufactured by sheeting or filming by a conventional process such as a T die process or extrusion. Embodiments of the present invention can be carried out in an in situ process using an apparatus in which the above-described production of a silane-modified olefin resin, an olefin resin composition comprising the same, and a filming or sheeting process are connected to each other. Can be.

Still other embodiments of the present invention also relate to an optoelectronic device comprising an optoelectronic device encapsulated by an encapsulant made from the olefin resin composition described above.

The optoelectronic device to be encapsulated may be, for example, a light emitting or light sensing site such as a photovoltaic cell, a light emitting diode or an organic light emitting diode.

The method of encapsulating the optoelectronic device using the specific structure of the optoelectronic device or the olefin resin composition according to the embodiments of the present invention is not particularly limited, and may be applied according to the purpose according to the device.

For example, when the optoelectronic device is a photovoltaic cell, the optoelectronic device may include the front substrates 11 and 21, the back sheets 12 and 22 and the front substrates 11 and 21, as shown in FIG. 1 or 2. And a solar cell module including photovoltaic elements 13 and 23 encapsulated by encapsulant 14 (a), 14 (b), and 24 between the back sheet 12 and 22. When the encapsulant may be prepared from the olefin resin composition according to the embodiments of the present invention.

The solar cell module as described above is manufactured by a conventional molding method such as a lamination method in which a front substrate, an encapsulant, a photovoltaic element, a back sheet, and the like are laminated according to a desired structure, and then heated and press-bonded while vacuum-integrating them as a unit. can do. In this case, the process conditions of the lamination method is not particularly limited, and can be generally performed for 1 minute to 30 minutes, or 1 minute to 10 minutes at a temperature of 90 ℃ to 230 ℃, or 110 ℃ to 200 ℃.

In the case of the olefin resin composition according to the embodiments of the present invention, a reactive silyl group, for example, a methoxysilyl group (Si-O-CH ₃ ), of the silane-modified olefin resin chemically unstable during the extrusion process may be During the modularization process, such as lamination, the hydrolysis catalyst is converted into silanol group (Si-OH) due to the hydrolysis catalyst included in the olefin resin composition, and chemicals by dehydration condensation with residues such as hydroxyl groups on the front substrate surface of the optoelectronic device Covalent bonds can be formed to show high adhesion.

In addition, the fluorine and silanol groups form hydrogen bonds at the interface with the back sheet having the surface layer containing fluoropolymers, which are widely used in recent years, thereby exhibiting high interfacial adhesion.

In the above, specific kinds of front substrate, back sheet, and photovoltaic element which can be used are not particularly limited. For example, the front substrate may be a conventional plate glass; Or a transparent composite sheet laminated with glass, a fluorine-based resin sheet, a weather resistant film, and a barrier film, and the back sheet may be a composite sheet laminated with a metal such as aluminum, a fluorine-based resin sheet, a weather resistant film, a barrier film, and the like. It has a surface layer containing a polymer. For example, it may be a multilayer film having a fluoropolymer layer formed on both sides of a polyethylene terephthalate (PET) film. In addition, the photovoltaic device may be, for example, a thin film active layer formed by a silicon wafer-based active layer or chemical vapor deposition (CVD).

In embodiments of the present invention, it can be used as an encapsulant of various optoelectronic devices, to provide an olefin resin composition with improved adhesion, in particular long-term adhesion properties and heat resistance with the front substrate and the back sheet included in the device. In addition, it is possible to provide an olefin resin composition and an encapsulant capable of maintaining excellent workability and economical efficiency of device manufacturing without adversely affecting parts and working environment such as an optoelectronic device or wiring electrode encapsulated in an optoelectronic device.

1 and 2 are cross-sectional views illustrating a solar cell module which is an optoelectronic device according to one example of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited by the following examples.

Example  One.

Manufacture of encapsulant

100 parts by weight polyethylene, 2.03 parts by weight of methacryloxypropyl trimethoxysilane, 0.01 parts by weight of acetic acid and 2,5-dimethyl having a density of 0.885 g / cm ³ and an MFR of 5 g / 10 min at 190 ° C. 0.1 parts by weight of -2,5-di (t-butylperoxy) hexane (2,5-dimethyl-2,5-di (tert-butylperoxy) hexane) was mixed in an extruder, followed by heating, melting and stirring at 200 캜. , A silane-modified polyethylene to which the methacryloxypropyl trimethoxysilane is grafted was prepared. As the olefin resin for addition, 100 parts by weight of linear low density polyethylene having a density of 0.885 g / cm ³ , 3 parts by weight of a hindered amine light stabilizer, 1 part by weight of a benzophenone UV absorber and 1 part by weight of a phosphorus thermal stabilizer are mixed. Then, 3 parts by weight of the master batch melted, processed and pelletized was introduced into the extruder using a side feeder, and then fed into a hopper of a film forming machine having a Φ 25 mm extruder and a T die of 300 mm width, and extruded. The sheet-like sealing material of about 500 micrometers in thickness was processed at the temperature of 200 degreeC, and the extraction speed | rate 3 m / min.

Manufacture of photovoltaic modules

Plate glass (thickness: about 8 mm), the encapsulant having a thickness of 500 μm, the crystalline silicon wafer photovoltaic device manufactured above, the encapsulant having a thickness of 500 μm, and a back sheet (polyvinyl fluoride resin sheet having a thickness of 38 μm, A laminated sheet of aluminum foil having a thickness of 30 μm and a polyvinyl fluoride resin sheet having a thickness of 38 μm) was laminated in this order, and pressed in a vacuum laminator at 150 ° C. for 15 minutes to produce a photovoltaic module.

Example  2.

An encapsulant and a photovoltaic module were prepared in the same manner except that 0.01 part by weight of stearic acid was used instead of 0.01 part by weight of acetic acid.

Example  3.

An encapsulant and a photovoltaic module were prepared in the same manner except that 0.2 part by weight of acetic acid was used instead of 0.01 part by weight of acetic acid in Example 1.

Example  4.

An encapsulant and a photovoltaic module were prepared in the same manner except in Example 1, that 0.05 parts by weight of acetic acid was used instead of 0.01 parts by weight of acetic acid.

Comparative Example  One.

An encapsulant and a photovoltaic module were prepared in the same manner except that acetic acid was not used in Example 1.

Comparative Example  2.

An encapsulant and a photovoltaic module were prepared in the same manner except in Example 1, 0.0001 parts by weight of acetic acid instead of 0.01 parts by weight of acetic acid.

Comparative Example  3.

An encapsulant and a photovoltaic module were prepared in the same manner except that 2 parts by weight of acetic acid was used instead of 0.01 parts by weight of acetic acid in Example 1.

Experimental Example

1. Measurement of 90 Degree Peel Strength

In order to measure the peel strength of the encapsulant prepared in Examples 1 to 4 and Comparative Examples 1 to 3, specimens similar to the prepared photovoltaic module were separately prepared. Specimens were plate glass (thickness: about 8 mm), the encapsulant having a thickness of 500 μm and the back sheet (38 μm thick polyvinyl fluoride resin sheet, 30 μm thick aluminum foil, and 38 μm thick polyvinyl fluoride resin) prepared above. Lamination of sheets) was laminated in order and prepared by lamination at 150 ° C. for 15 minutes in a vacuum laminator. After fixing the lower glass plate of the prepared specimen, the peel strength measured while peeling the encapsulant adhered only to the back sheet at the speed of 4.2 mm / sec and a 90 degree peel angle at the same time as the back sheet according to ASTM D1897. Shown in

2. Evaluation of Sheet Formability

 The surface of the sealing material processed in the said Examples 1-4 and Comparative Examples 1-3 was evaluated, and sheet formability was evaluated, and it is shown in following Table 1.

Furtherance 90 degree peel strength (N / 15mm) Sheet Formability Example 1 Acetic acid 0.01 103.6 Good Example 2 Stearic Acid 0.01 88.3 Good Example 3 Acetic acid 0.2 88.3 Good Example 4 Acetic acid 0.05 81.4 Good Comparative Example 1 - 74.8 Good Comparative Example 2 Acetic acid 0.0001 76.5 Good Comparative Example 3 Acetic acid 2 64.0 Bad

As shown in Table 1, when using an olefin resin composition containing 0.01 to 1 parts by weight of a hydrolysis catalyst (Examples 1 to 4), it can be seen that exhibits good adhesive properties. However, if no hydrolysis catalyst is used (Comparative Example 1), if the content is below or above a certain level (Comparative Examples 2 and 3), problems may occur due to poor adhesion or gel formation on the surface during sheet forming. It can be confirmed.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be appreciated that other embodiments are possible. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

1, 2: Solar cell module
11, 21: front substrate
12, 22: back sheet
13, 23: photovoltaic device
14 (a), 14 (b), 24: encapsulant

Claims (22)

An olefin resin, an unsaturated silane compound of Formula 1, a hydrolysis catalyst, and a radical initiator,
An olefin resin composition comprising 0.001 to 1 part by weight of the hydrolysis catalyst based on 100 parts by weight of the olefin resin:
[Chemical Formula 1]
DSi (X) _m Y _(3-m)
In Formula 1, D represents alkenyl as bonded to a silicon atom,
X is bonded to a silicon atom and represents an alkoxy group, phenoxy group, alkylthio group, aryloxy group, acyloxy group, halogen group, amine group or alkyleneoxythio group,
Y is bonded to a silicon atom and represents hydrogen, an alkyl group, an aryl group or an aralkyl group,
m represents the integer of 1-3. The olefin resin composition according to claim 1, wherein the hydrolysis catalyst is an acid catalyst. The method of claim 1, wherein the hydrolysis catalyst is hydrochloric acid, phosphoric acid (sulfuric acid), sulfuric acid (sulfuric acid), nitric acid (Nitric acid), chromic acid (Chromic acid), stearic acid (acetic acid), acetic acid (acetic acid), sulfonic acid (sulfonic acid), citric acid, lactic acid, gluconic acid, glycolic acid, glycolic acid, succinic acid, oxalic acid, benzoic acid, tartaric acid (Tartaric acid), Fumaric acid, Mandelic acid, Propionic acid, Maleic acid, Maleic acid, Galacturonic acid, Glutamic acid, Glutaric acid acid), glucuronic acid, aspartic acid, ascorbic acid, carboxylic acid, carboxylic acid, vanillic acid, and hydroiodic acid. 1 or more types of olefin resin composition selected. The olefin resin composition according to claim 1, wherein the olefin resin is polyethylene. The olefin resin composition of claim 4, wherein the polyethylene has a density of 0.85 g / cm ³ to 0.92 g / cm ³ . The olefin resin composition according to claim 4, wherein the polyethylene has an MFR of 1.0 g / 10 min to 10.0 g / 10 min at 190 ° C. The olefin resin composition according to claim 1, wherein X represents an alkoxy group having 1 to 12 carbon atoms. The olefin resin composition according to claim 1, wherein the unsaturated silane compound of Formula 1 is vinyl alkoxy silane. The method of claim 1, wherein the unsaturated silane compound is vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl tributoxy silane, vinyl tripentoxy silane, vinyl tree The olefin resin composition which is phenoxy silane or vinyl triacetoxy silane. The olefin resin composition of claim 1, wherein the unsaturated silane compound of Formula 1 is included in an amount of 0.1 parts by weight to 5.0 parts by weight based on 100 parts by weight of the olefin resin. The olefin resin composition according to claim 1, wherein the radical initiator is one or two or more selected from the group consisting of organic peroxides, hydroperoxides and azo compounds. 12. The method of claim 11, wherein the radical initiator is at least one selected from the group consisting of t-bubulcyl cumyl peroxide, di-t-butyl peroxide, , 2,5-dimethyl-2,5-di (t -peroxy) hexane, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5- t-butyl hydroperoxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, Butyl peroxyacetate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxy octoate, t-butylperoxyisopropyl carbonate butyl peroxybenzoate, di-t-butylperoxy phthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5- C) hexine, methyl ketone peroxide, cyclohexanone peroxide, lauryl peroxide, azobisisobutyronitrile, and at least one olefin resin selected from the group consisting of azobis (2,4-dimethylvaleronitrile) Composition. The olefin resin composition of claim 1, wherein the radical initiator is included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the olefin resin. The olefin resin composition of claim 1, further comprising at least one additive selected from the group consisting of a light stabilizer, a UV absorber, and a heat stabilizer. A silane-modified olefin resin and a hydrolysis catalyst,
An olefin resin composition in which the silane-modified olefin resin has a reactive silyl group represented by Formula 2 below:
(2)
-Si (X) _m Y _(3-m)
In Formula 2, X is bonded to a silicon atom, an alkoxy group, phenoxy group, alkylthio group, aryloxy group, acyloxy group, halogen group, amine group or alkyleneoxythio group or any one of the above Represent decomposition products,
Y is bonded to a silicon atom and represents hydrogen, an alkyl group, an aryl group or an aralkyl group,
m represents the integer of 1-3. The method of claim 15, wherein the hydrolysis catalyst is hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, chromic acid, stearic acid, acetic acid, sulfonic acid. (sulfonic acid), citric acid, lactic acid, gluconic acid, glycolic acid, glycolic acid, succinic acid, oxalic acid, benzoic acid, tartaric acid (Tartaric acid), Fumaric acid (Fumaric acid), Mandelic acid, Propionic acid, Maleic acid, Maleic acid, Galacturonic acid, Glutamic acid, Glutaric acid acid), glucuronic acid, aspartic acid, ascorbic acid, carboxylic acid, carboxylic acid, vanillic acid, and hydroiodic acid. 1 or more types of olefin resin composition selected. The olefin resin composition according to claim 15, further comprising an olefin resin for addition. Encapsulant for optoelectronic devices comprising the olefin resin composition according to claim 15. Adding an olefin resin, an unsaturated silane compound of formula 1, a hydrolysis catalyst and a radical initiator into the reactor;
Preparing an olefin resin composition of claim 15 by grafting the unsaturated silane compound to an olefin resin; And
Method for producing an encapsulant for an optoelectronic device comprising the step of molding the olefin resin composition into a film or sheet shape:
[Chemical Formula 1]
DSi (X) _m Y _(3-m)
In Formula 1, D represents alkenyl as bonded to a silicon atom,
X is bonded to a silicon atom and represents an alkoxy group, phenoxy group, alkylthio group, aryloxy group, acyloxy group, halogen group, amine group or alkyleneoxythio group,
Y is bonded to a silicon atom and represents hydrogen, an alkyl group, an aryl group or an aralkyl group,
m represents the integer of 1-3. 20. The method of manufacturing an optoelectronic device encapsulation according to claim 19, wherein the method for manufacturing an encapsulation material for an optoelectronic device is performed in an in situ process using devices connected to each other. A front substrate, an encapsulant for an optoelectronic device according to claim 18, an optoelectronic device and a back sheet;
The back sheet comprises a surface layer containing a fluoropolymer,
An optoelectronic device in which a hydrogen bond is formed at an interface between the encapsulant for the optoelectronic device and the back sheet. Laminating a front substrate, an encapsulant for optoelectronic devices, an optoelectronic device and a back sheet according to claim 18; And
Vacuum laminating the laminate;
The back sheet includes a surface layer containing a fluoropolymer, and the hydrolysis-promoting reaction of the alkoxy group, acyloxy group, halogen group or amine group of the optoelectronic device encapsulation occurs by the hydrolysis catalyst to encapsulate the optoelectronic device. The manufacturing method of the optoelectronic device in which the adhesive strength of the interface of a back sheet is improved.

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